Atomic motion in Se nanoparticles embedded into a porous glass matrix

By neutron diffraction it was shown that nanostructured Se confined within a porous glass matrix exists in a crystalline as well as in an amorphous state. The spontaneous crystallization of crystalline Se from confined amorphous phase was observed. The root-mean-square amplitudes of the atomic motions in the bulk as well as in confinement are found to be essentially different in a basal plane and in the perpendicular direction along the hexagonal axis. The atomic motions in the confined Se differ from the atomic motions in the bulk at low temperatures. The results shows an unusual “freezing" of the atomic motion along the chains, while the atomic motions in the perpendicular plane still keep. This “freezing" is accompanied by the deformation of nanoparticles and the appearance of inner stresses. This effect is attributed to the interaction of confined nanoparticle with the cavity walls.     

Growth of crystalline/amorphous biphase Sm-Fe-Ta-N magnetic nanodroplets

Thin films of biphase (amorphous/crystalline) magnetic Sm-Fe-Ta-N nanodroplets were fabricated at room temperature with 157 nm pulse laser deposition in nitrogen from a Sm_13.8Fe_82.2Ta_4.0 target. The 50-100 nm biphase spherical nanodroplets consist of a 5-10 nm internal crystal portion surrounded by the external amorphous phase. Nitrogen fixation in the nanodroplets occurred in the plume. The films exhibit a ferromagnetic response of 2.5 kOe coercivity at room temperature. With further annealing and thermal treatment in nitrogen, the coercivity was increased to 5.0 kOe. The surrounding amorphous layer prevents post-ablation oxidization of the crystalline magnetic nucleus of the nanodroplet.     

Evolution of magnetic order in mechanically alloyed Al–1 at%Fe

The evolution of ferromagnetic order in high-energy ball-milled Al–1 at% Fe before the onset of a considerable Fe–Al solid solution phase has been investigated using ⁵⁷Fe Mössbauer and bulk magnetization studies. The unmilled sample does not exhibit bulk magnetic properties and an onset of bulk magnetization is observed only after 30 min of milling, when the grain size becomes comparable to the ferromagnetic exchange length. The Curie temperatures of all the samples are less than that of pure iron. The reduction in grain size is accompanied by an increase in coercivity and reduced remanence and a decrease in T_C. The effective magnetic moment per iron atom decreases with the development of a non-magnetic, Al-rich Fe–Al solution on longer milling. The clustering of Fe at grain boundaries is responsible for the observed bulk magnetic ordering. The systematic variation of the magnetic properties has been qualitatively correlated with the evolution of microstructure, reduction in grain size and enhanced inter-granular exchange coupling.     

Thermodynamic properties of small amorphous and crystalline Silica particles at low temperatures

We have measured the low-temperature (K) specific heat and heat release of small amorphous and crystalline SiO₂ particles embedded in Teflon and of Vycor. The temperature and time dependence of these properties have been interpreted in terms of the tunneling model. We found that the particle size influences the density of states of tunneling systems of the composite. The smaller the size of the particles the larger is the density of states of tunneling systems P₀. Quartz grains with dimensions in the micrometer range show similar glass-like properties as vitreous silica. In comparison with bulk vitreous silica, Vycor shows a much larger P₀ in agreement with the behavior we found for small SiO₂ particles. We discuss the implication of our results on the origin of the universal low-temperature properties of glasses. Received 9 April 1998     

Crystalline and relaxation properties of ethylene copolymer films inserted between two steel sheets

The relaxation and crystalline properties of ethylene vinyl acetate (EVA) co-polymers inserted in steel/polymer/steel assemblies were studied. To investigate the properties of the interfacial region, polymers of different thickness inserted in the assemblies were analyzed. The studied EVA copolymers are semicrystalline polymers. The relaxation properties of the amorphous phase were investigated by dynamic mechanical measurements performed on the steel/polymer/steel assemblies, and the crystalline properties were studied by differential scanning calorimetry (DSC). The results indicate that, for low polymer thicknesses, the mobility of the amorphous phase is significantly reduced. Significant changes in the crystalline organization also were observed when the polymer thickness decreased, with the presence of more numerous disorganized crystals for thin EVA layers. These crystals can act as physical ties that reduce the mobility of the neighboring amorphous chains. These results indicate the formation of an interphase layer of reduced mobility.     

Microstructural and optical investigations of sol-gel derived ferroelectric BaTiO3 nanocrystalline films determined by spectroscopic ellipsometry

Ferroelectric BaTiO₃ nanocrystalline films (BTNFs) with the crystalline sizes of about 30 nm were grown on Pt/Ti/SiO₂/Si substrates by a modified sol-gel method. Spectroscopic ellipsometry (SE) was used to characterize the films in the photon energy range of 1.5-5.0 eV with a five-phase layered model (air/surface rough layer/BaTiO₃/interface layer/Pt). The optical properties in the transparent and absorption regions have been investigated with the Forouhi-Bloomer dispersion relation. With the aid of the structural and dielectric function models, the microstructure and electronic structure of the BTNFs can be readily obtained. It was found that the refractive index reaches the value of 2.20 in the transparent region. Based on the Sellmeier dispersion analysis, the single-oscillator energy is about 4.7 eV for the BTNFs. The long wavelength refractive index n(0) can be estimated to about 2.00 at zero point. The direct optical band gap energy approaches approximately 4.2 eV and Urbach band tail energy is 262±2 and 268±1 meV respectively with increasing crystalline size. A higher band gap observed can be owing to the known quantum confinement effect in the nanocrystalline formation and different fraction of amorphous and crystalline components. The theoretical analysis based on the effective mass approximation theory is well used to explain these experimental data.     

Microstructure evolution in Pr-Co-C-Ti nanophase magnets

The microstructures of nanophase Pr-Co-C-(Ti) materials, which have improved magnetic properties, were investigated by means of transmission electron microscopy (TEM) to reveal their phase assemblage and grain-boundary structure. The phase assemblage was carefully controlled by the introduction of TiC nanoparticles and annealing. The optimal nanostructure contained uniformly distributed PrCo₅ and PrCo₂ nanophases without any magnetically soft phases, resulting in high coercivity and the characteristics of a single, hard magnetic phase. TEM analysis confirmed the presence of an amorphous grain-boundary phase surrounding the grains in alloys without TiC. In contrast, alloys with added TiC showed no amorphous phase and also showed higher coercivity compared to Co-Pr-C. Therefore, the variation of the grain boundary phases may be effective in changing the degree of exchange coupling. Controlling the formation of a uniform nanoscale microstructure, leading to improved magnetic properties, is discussed. Received: 5 September 2002 / Accepted: 10 September 2002 / Published online: 22 January 2003 RID="*" ID="*"Corresponding author. Fax: +1-630/252-7777, E-mail: ytang@anl.gov     

Morphologies of diblock copolymer thin films before and after crystallization

Spin-coated thin films of about 100nm of low-molecular-weight hydrogenated poly(butadiene-b- ethyleneoxide) (PB_h-PEO) diblock copolymers have been crystallized at various constant temperatures. Crystallization has been observed in real time by light microscopy. Detailed structural information was obtained by atomic force microscopy, mainly enabled by the large viscoelastic contrast between amorphous and crystalline regions. The behavior in thin films is compared to the bulk properties of the polymer. Crystallization started from an annealed microphase separated melt where optical microscopy indicated a lamellar orientation parallel to the substrate. A small difference in the length of the crystallizable block produced significantly different crystallization behavior, both in the bulk and in thin films. For thin films of the shortest diblock copolymer (45% PEO content) and for an undercooling larger than about 10 degrees, crystallization created vertically oriented lamellae. These vertical lamellae could be preferentially aligned over several micrometers when crystallization occurred close to a three-phase contact line. Annealing at temperatures closer to the melting point or keeping the sample at room temperature for several months allowed the formation of a lamellar structure parallel to the substrate. A tentative interpretation based on kinetically caused chain folding and relaxation within the crystalline state, with implications on general aspects of polymer crystallization, is presented. Received 19 March 1999 and Received in final form 14 December 1999     

Effects of structure on exchange interactions in crystalline and amorphous alloys GdxY50−xAg50

Magnetic interactions and effects of dilution with nonmagnetic Y on the magnetic properties of crystalline and amorphous alloys Gd_xY_50−xAg₅₀ (10 ≤ x ≤ 50) have been investigated by measurements of bulk magnetization and susceptibility and by Mössbauer spectroscopy with ¹⁵⁵Gd. The crystalline alloys order antiferromagnetically for all Gd concentrations with a noncollinear arrangement of Gd moments induced by negative biquadratic exchange interactions. In amorphous alloys, ferromagnetic order is found for large Gd concentrations (x ≥ 40). Below the critical concentration x_cr, in the range 30<x_cr<40, properties typical for magnetic cluster glasses are observed. Magnetic hyperfine fields B_hf at ¹⁵⁵Gd nuclei vary with x in opposite directions in amorphous and in crystalline alloys. In crystalline alloys, the variation is due to a positive transferred hyperfine field. In amorphous alloys, a reduction of |B_hf| with decreasing Gd concentration is caused by a reduction of the frozen Gd moments in the cluster glass phase.     

Magnetostatic properties of heterogeneous Co-based amorphous/crystalline phases

Using the magneto-optical Kerr effect, magnetic hysteresis loops are measured on annealed amorphous Co₆₆Fe₄B₁₅Si₁₅ samples, to characterize the magnetostatic properties of the heterogeneous crystalline/amorphous phases. A gradual change, on microscale inhomogeneous, change of the magnetic properties with respect to thickness is revealed on HCP-Co, FCC-Co crystalline phases near the surface. The inner amorphous phase exhibits an irregular variation of the local magnetic properties, presumably due to the occurrence and distribution of microcrystallites. The effective field, exerted by the crystalline layer on the amorphous phase, is opposite to the surface magnetization, indicating that there is an antiferromagnetic coupling between surface and inner amorphous phases.     

Freezing behavior of one-dimensional copper nanowires

The freezing behavior of copper nanowires at different cooling rates was studied by using molecular dynamics (MD) simulation via embedded atom methods (EAM) potential. The simulation results indicate that the structure of the nanowires changed from amorphous to crystalline via helical multi-shelled structure with decreasing cooling rates. The curves of the energy-temperature and the local clusters were used to study the phase transition. The variation of local clusters implies that the order of the system increases as the temperature drops. The fcc crystalline structure of the copper nanowires with the diameter of 1.63 nm was proved to be the most stable form.     

Compression Behaviour of Bulk Metallic Glasses and Binary Amorphous Alloy

The compression properties of Zr41Ti14Cu12.aNi10Be22.5, Zr44.4Nb7Cu13.5Ni10.8Be24.3 bulk metallic glasses and Ni77P23 binary amorphous alloy are investigated at room temperature up to 24 GPa, 39 GPa and 30.5 GPa, respectively, using in-situ high pressure energy dispersive x-ray diffraction with a synchrotron radiation source. The pressure-volume relationship of Ni77P23 amorphous alloy is consistent well with the second order BirchMurnaghan （B-M） equation within the experimental pressure range. However, under higher pressure, the experimental data of Zr-based specimens deviate from the B-M equation. Compare to the binary amorphous alloy less excess free volume existing in the bulk metallic glass and multi-component atomic configuration results in a two-stage relationship between compressibility and pressure.     

Thermomechanical properties of amorphous hydrogenated carbon–germanium alloys

Thermomechanical properties of amorphous hydrogenated carbon-germanium alloys prepared by the rf sputtering technique were determined for films in the 0 at. % to 100 at. % carbon content range. The stress, thermal expansion coefficient, and elastic modulus were obtained using the thermally induced bending technique. The stress was related to the concentration of hydrogen and argon, to the difference in the Ge-Ge and Ge-C bond length, and to the carbon hybridization. The thermal expansion coefficients of pure amorphous germanium and amorphous carbon are higher than that of their corresponding crystalline counterparts, which was attributed to the compressive stress of the films. The biaxial modulus, on the other hand, are always smaller than that of their crystalline counterparts, but increases as the concentration of carbon increases due to the substitution of Ge-Ge bonds by energetically stronger Ge-C and C-C bonds. Received: 9 May 2000 / Accepted: 10 May 2000 / Published online: 13 July 2000     

Theoretical analysis of optical properties of dielectric coatings dependence on substrate subsurface defects

A model for refractive index of stratified dielectric substrate was put forward according to theories of inhomogeneous coatings. The substrate was divided into surface layer, subsurface layer and bulk layer along the normal direction of its surface. Both the surface layer (separated into N₁ sublayers of uniform thickness) and subsurface layer (separated into N₂ sublayers of uniform thickness), whose refractive indices have different statistical distributions, are equivalent to inhomogeneous coatings, respectively. And theoretical deduction was carried out by employing characteristic matrix method of optical coatings. An example of mathematical calculation for optical properties of dielectric coatings had been presented. The computing results indicate that substrate subsurface defects can bring about additional bulk scattering and change propagation characteristic in thin film and substrate. Therefore, reflectance, reflective phase shift and phase difference of an assembly of coatings and substrate deviate from ideal conditions. The model will provide some beneficial theory directions for improving optical properties of dielectric coatings via substrate surface modification.     

Investigation of thermal annealing effects on microstructural and optical properties of HfO2 thin films

In the present paper, we investigate the effect of thermal annealing on optical and microstructural properties of HfO₂ thin films (from 20 to 190 nm) obtained by plasma ion assisted deposition (PIAD). After deposition, the HfO₂ films were annealed in N₂ ambient for 3 h at 300, 350, 450, 500 and 750 °C. Several characterisation techniques including X-ray reflectometry (XRR), X-ray diffraction (XRD), spectroscopic ellipsometry (SE), UV Raman and FTIR were used for the physical characterisation of the as-deposited and annealed HfO₂ thin films. The results indicate that as-deposited PIAD HfO₂ films are mainly amorphous and a transition to a crystalline phase occurs at a temperature higher than 450 °C depending on the layer thickness. The crystalline grains consist of cubic and monoclinic phases already classified in literature but this work provides the first evidence of amorphous-cubic phase transition at a temperature as low as 500 °C. According to SE, XRR and FTIR results, an increase in the interfacial layer thickness can be observed only for high temperature annealing. The SE results show that the amorphous phase of HfO₂ (in 20 nm thick samples) has an optical bandgap of 5.51 eV. Following its transition to a crystalline phase upon annealing at 750 °C, the optical bandgap increases to 5.85 eV.     

Mössbauer spectroscopy studies of spin reorientations in amorphous and crystalline (Co0.2Fe0.8)72.5Si12.5B15 glass coated micro-wires

Thermo-gravimetric, differential scanning calorimetry and comprehensive ⁵⁷Fe Mössbauer spectroscopy studies of amorphous and crystalline ferromagnetic glass coated (Co_0.2Fe_0.8)_72.5Si_12.5B₁₅ micro-wires have been recorded. The Curie temperature of the amorphous phase is T_C(amorp) ∼730 K. The analysis of the Mössbauer spectra reveals that below 623 K the easy axis of the magnetization is axial-along the wires, and that a tangential or/and radial orientation occurs at higher temperatures. At 770 K, in the first 4 hours the Mössbauer spectrum exhibits a pure paramagnetic doublet. Crystallization and decomposition to predominantly α-Fe(Si) and Fe₂B occurs either by raising the temperature above 835 K or isothermally in time at lower temperatures. Annealing for a day at 770 K, leads to crystallization. In the crystalline material the magnetic moments have a complete random orientation. After cooling back to ambient temperature, both α-Fe(Si) and Fe₂B in the glass coated wire show pure axial magnetic orientation like in the original amorphous state. The observed spin reorientations are associated with changes in the stress induced by the glass coating.     

Influence of tensile deformation on the crystalline organization of ethylene copolymers

The influence of tensile deformation on the crystalline properties of ethylene copolymers (ethylene-vinyl acetate [EVA] copolymers) was investigated by differential scanning calorimetry (DSC). The consequence of drawing on the mobility of the amorphous phase also was investigated through the study of the glass transition temperature. The results indicate that more disorganized crystals, melting at a lower temperature, are present after the tensile deformation, reducing the mobility of the amorphous chains, as shown by an increase of the glass transition temperature. For the lowest molecular weight copolymer. less crystalline changes are observed after the tensile test, probably due to the fact that no stiffening appears during the drawing.     

Formation of budesonide/α-lactose glass solutions by ball-milling

The possibility to obtain amorphous budesonide stabilised by blending with an excipient characterised by a higher glass transition temperature, namely α-lactose, has been studied. We carried out the mixing of the two compounds at room temperature by ball-milling. The four obtained blends (containing, respectively, 10, 30, 50 and 70%_w of budesonide) are X-ray amorphous and exhibit a single glass transition located between the ones of pure milled crystalline compounds. This revealed that the two amorphous phases are miscible whatever the composition and sufficiently mixed to relax as a whole. Ball-milling thus appears as a powerful tool to form amorphous molecular alloys with enhanced stability properties.     

External influence on magnetic properties of Fe-based nanocrystalline alloys

Amorphous and nanocrystalline ribbons of NANOPERM, FINEMET and HITPERM were studied by Mössbauer spectroscopy (MS) after the influence of external factors: different annealing atmospheres, tensile stress and several kinds of corrosion. MS is a suitable tool for such studies because the spectral parameters are very sensitive to changes in the vicinity of the probe — ⁵⁷Fe nuclei. The most sensitive parameters were hyperfine magnetic field in crystalline component, average hyperfine field in amorphous component and direction of net magnetic moments. Influence of external factors modified also the structure of the alloys, i.e. new or modified phases were identified by MS phase analysis.     

Surface characterization of amorphous and crystallized Fe80B20

Recent studies of catalysis by amorphous metals have prompted an interest in their surface properties. We have utilized Auger electron spectroscopy, X-ray photoelectron spectroscopy and low energy alkali ion scattering to study the surface composition, electronic properties and topography of amorphous and crystallized Fe₈₀B₂₀ ribbons. The majorresults are that the surface stoichiometry is approximately that of the bulk, unaltered by segregation. Bulk crystallization results in the diffusion of impurities to the surface, but does not change the Fe/B ratio. A small shift in the B1s core level binding energy was observed on crystalline, annealed surfaces relative to amorphous or sputtered surfaces, but no shifts were observed in the iron core level energies. A weak feature due to the B2p levels was observed in the valence band spectra from sputtered surfaces. The surfaces exhibit atomic scale roughness which is not altered by bulk crystallization. Finally, there were no observable differences in the structure, composition or electronic properties between the two sides of the ribbons.